JP5941476B2 - Process for the polymerization of olefins using extracted metal carboxylate salts - Google Patents

Process for the polymerization of olefins using extracted metal carboxylate salts Download PDF

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JP5941476B2
JP5941476B2 JP2013542013A JP2013542013A JP5941476B2 JP 5941476 B2 JP5941476 B2 JP 5941476B2 JP 2013542013 A JP2013542013 A JP 2013542013A JP 2013542013 A JP2013542013 A JP 2013542013A JP 5941476 B2 JP5941476 B2 JP 5941476B2
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catalyst
metal carboxylate
carboxylate salt
extracted
compound
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JP2014501814A (en
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アール・エリック・ペケーニョ
ファティ・デイビッド・フセイン
ケヴィン・ジョセフ・カン
チー−イー・クオ
ブルース・ジョン・サバトスキ
エリック・ジェイ・マーケル
ダニエル・ポール・ジルカー・ジュニア
アガピオス・キリアコス・アガピオウ
デーヴィッド・エム・グロウチェウスキー
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ユニベーション・テクノロジーズ・エルエルシー
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    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
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    • C08F4/65922Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
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    • C08F4/65927Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943Polymerization with metallocene catalysts

Description

Technical field and background technology

  Metallocene catalysts are widely used to produce polyolefin polymers such as polyethylene polymers. They have provided efficient methods and a variety of new and improved polymers. However, there is a continuing focus in the industry on developing new metallocene catalyst compositions and improved metallocene catalyst compositions. Some focus on designing catalyst compositions to produce new polymers, others focus on improving operability, and others improve catalyst productivity. Focus on. Catalyst productivity, ie the amount of polymer produced per gram of catalyst, can be a significant concern for polyolefin manufacturers. Reactor operability (eg, no fouling or sheeting) is another major concern for polyolefin manufacturers. Reducing the occurrence of reactor fouling is industrially beneficial in that reactor downtime is reduced, polyolefin resin production increases, and high quality resins are obtained.

  To address reactor fouling problems, other additives such as metal carboxylate salts are often added separately or as part of the supported catalyst composition to the catalyst. However, such additives may suppress catalyst productivity and resin bulk density.

  Accordingly, it would be advantageous to have an improved polymerization process utilizing metal carboxylate salts to address reactor fouling problems, for example, without undesirable suppression of catalyst productivity and resin bulk density. .

SUMMARY Disclosed herein is a method for olefin polymerization using extracted metal carboxylate salts. This method may be characterized by having increased catalyst productivity and / or increased resin bulk density. The polymerization process can include polymerizing the olefin in the reactor in the presence of the catalyst composition and the extracted metal carboxylate salt, wherein the extracted metal carboxylate salt is 3.0 Or it was obtained by extracting metal carboxylate salt with the organic solvent which has the dielectric constant more than it. The extracted metal carboxylate salt can be added to the reactor together with the catalyst composition or separately from the catalyst composition.

  Also a polymerization process for producing ethylene / α-olefin copolymers with increased catalyst productivity and / or increased resin bulk density, wherein the ethylene / α-olefin copolymer is produced in a reactor. Contacting the ethylene and α-olefin with a catalyst composition under polymerization conditions for the catalyst composition comprising a polymerization catalyst and a first extracted metal carboxylate salt, the first extracted Also provided is the polymerization process, wherein the metal carboxylate salt is obtained by extracting the metal carboxylate salt with an organic solvent having a dielectric constant of 3.0 or higher at 25 ° C. The method can further include adding a continuous additive comprising a second extracted metal carboxylate salt to the reactor, wherein the second extracted metal carboxylate salt is combined with the catalyst composition. Is added separately to the reactor, and this second extracted metal carboxylate salt is obtained by extracting the metal carboxylate salt with an organic solvent having a dielectric constant of 3.0 or higher at 25 ° C. It is what was done.

DETAILED DESCRIPTION Before disclosing and explaining the compounds, components, compositions and / or methods of the present invention, unless otherwise indicated, the present invention is directed to specific compounds, components, compositions, reaction components, reaction conditions, ligands, It should be understood that the structure is not limited to a metallocene structure and the like, and can be changed unless otherwise specified. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting.

  In addition, it should be understood that the singular expression used in the present specification and claims includes a plurality of cases unless otherwise specified. Thus, for example, reference to a “leaving group” as in a “substituted with a leaving group” includes more than one leaving group, and that portion is substituted with two or more such groups. It may be. Similarly, when referring to a “halogen atom” as in a “substituted by halogen” moiety, it also includes more than one halogen atom, and that moiety may be substituted with two or more halogen atoms. Often, "substituent" includes one or more substituents, "ligand" includes one or more ligands, and so on.

  As used herein, all references to the Periodic Table of Elements and their families are in HAWLEY'S CONDENSED CHEMICAL DICTIONARY, 13th edition, John Wiley and Sons (1997), a new notation (with authorization from IUPAC) (Reproduced there), except when referring to the previous IUPAC shown in Roman numerals (which also appears in the same) or where otherwise specified.

  Disclosed herein are olefin polymerization processes having increased catalyst productivity and / or increased resin bulk density. Particular methods disclosed include those relating to the polymerization of olefins in the presence of a metallocene catalyst compound and an extracted metal carboxylate salt. In some embodiments, the metal carboxylate salt and the metallocene catalyst compound can be added separately to the reactor. Also disclosed herein is a catalyst composition comprising a metallocene catalyst compound and an extracted metal carboxylate salt and having enhanced catalyst productivity. Also disclosed herein are metallocene catalyst compounds produced by the Incipient Wetness technology. Furthermore, a method for producing a catalyst composition and a polymer product produced by the polymerization method are also disclosed.

  In some of the embodiments disclosed herein, it has been found that using an extracted metal carboxylate salt in combination with a catalyst compound results in increased catalyst productivity. It has further been found that higher resin bulk density can be provided by using extracted metal carboxylate salts in combination with catalyst compounds. Higher resin bulk density is much higher, including higher plant speeds and higher monomer efficiency (eg, less ethylene vented to flare) and environmental credit guarantees to reduce ethylene emissions. May be advantageous for the reasons described above. Furthermore, it has been found that enhanced catalyst productivity can also be obtained by using a metallocene catalyst compound produced by impregnating incipient wetness.

Extracted Metal Carboxylate Salts In the polymerization of olefins described herein, extracted metal carboxylate salts can be used. The extracted metal carboxylate salt can be obtained by extracting the metal carboxylate salt with an organic solvent having a dielectric constant of 3.0 or more at 25 ° C. As used herein, the term “metal carboxylate salt” refers to any mono- or di- or tri-carboxylate salt with a metal moiety from the periodic table of elements. Without being bound by theory, the extraction of the metal carboxylate salt may reduce or even remove the free carboxylic acid or derivative thereof that normally remains as a residue after synthesis of the metal carboxylate salt. Believable. The reduced catalyst productivity and resin bulk density that occur as a result of using a metal carboxylate salt with a metallocene catalyst, at least in part, is the free carboxylic acid present in the metal carboxylate salt or the group 1 or group 2 thereof. This is due to the salt fraction.

  In certain embodiments, the extracted metal carboxylate salt should be substantially free of free carboxylic acid. As used herein, the term “substantially free of free carboxylic acid” means that the extracted metal carboxylate salt has a melting corresponding to the free acid or its group 1 or group 2 salt in DSC analysis. Says not showing temperature (melting point). The extracted metal carboxylate salt has a total free acid of about 1% by weight or less based on the total weight of the metal carboxylate salt extracted as measured by chromatography, or the total weight of the extracted metal carboxylate salt. It can have a total free acid of no more than about 0.5% by weight, or no more than about 0.1% by weight.

The extracted metal carboxylate salt can be obtained by extracting the metal carboxylate salt with an organic solvent having a dielectric constant of 3.0 or higher at 25 ° C. This polar solvent provides improved extraction of polar compounds including free acids present in the crude metal carboxylate salt. Examples of suitable organic solvents, C 1 -C 10 alcohol, C 1 -C 10 ketones, C 1 -C 10 esters, C 1 -C 10 ethers, C 1 -C 10 alkyl halide, C 1 -C 10 alkyloxycarbonyl nitrile, C 1 -C 10 dialkyl sulfoxides and their combinations are encompassed. In another embodiment, the organic solvent is methanol, ethanol, propanol, isopropanol, butanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, methyl propionate, methyl buterate, dimethyl ether, diethyl ether, 1,4-dioxane. , Tetrahydrofuran, chloroform, dichloromethane, acetonitrile, dimethyl sulfoxide and combinations thereof.

The dielectric constant of the solvent is defined by ε in the following equation:
F = (QQ ′) / (εr 2 )
Where F is the attractive force between two charges Q and Q ′ separated by a distance r in the solvent. The dielectric constants of many solvents are well known and can be found, for example, on pages E-55 to E-62 of the CRC Handbook of Chemistry and Physics 59th edition.

  Preferred solvents are those having a dielectric constant at 25 ° C. of 3 or more, 5 or more, 7 or more, 10 or more, 12 or more, 15 or more, or 17 or more. In certain embodiments, the solvent can have a dielectric constant at 25 ° C. of at least 20.

  Non-limiting examples of metal carboxylate salts that can be used as precursors for extracted metal carboxylate salts include saturated, unsaturated, aliphatic, aromatic or saturated cyclic carboxylates. Non-limiting examples of carboxylate ligands include acetate, propionate, butyrate, valerate, pivalate, caproate, isobutyl acetate, t-butyl acetate, caprylate, heptanoate, pelargonate, undecanoate, oleate, octoate, palmitate, myristate , Margarate, stearate, arachate and tercosanoate. Non-limiting examples of metal parts include Al, Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li from the periodic table of elements and There are metals selected from the group of Na.

The metal carboxylate salt can be represented by the following general formula:
M (Q) x (OOCR) y
(Where M is a metal from group 3-16 and the lanthanide and actinide series, or a metal from group 8-13, or a metal from group 13, one specific example being aluminum. ;
Q is a halogen, hydrogen, hydroxy or hydroxide, alkyl, alkoxy, aryloxy, siloxy, silane or sulfonate group;
R is a hydrocarbyl group having 1 to 100 carbon atoms;
x is an integer of 0 to 3, y is an integer of 1 to 4, and the sum of x and y is equal to the valence of the metal. )

  R in the above formula may be the same or different. Non-limiting examples of R include hydrocarbyl groups having 2 to 100 carbon atoms, including alkyl, aryl, aromatic, aliphatic, cyclic, saturated or unsaturated hydrocarbyl groups. . In certain embodiments, R is a hydrocarbyl group having 8 or more carbon atoms, or 12 or more carbon atoms, or more than 14 carbon atoms. In another embodiment, R can comprise a hydrocarbyl group having 17-90 carbon atoms, or 17-72 carbon atoms, or 17-54 carbon atoms. In another embodiment, R comprises 6-30 carbon atoms, or 8-24 carbon atoms, or 16-18 carbon atoms (eg, palmityl and stearyl).

  Non-limiting examples of Q in the above formula include alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl, alkylsilane, arylsilane, alkylamine, arylamine, alkylphosphide, alkoxy One or more of the same or different hydrocarbons containing groups such as (having 1 to 30 carbon atoms) are included. The hydrocarbon-containing group may be linear or branched, and may be further substituted. Q can also be an inorganic group such as a halide, sulfate or phosphate.

The metal carboxylate salts can include aluminum carboxylates such as aluminum mono-, di- and tristearate, aluminum octoate, oleate and cyclohexyl butyrate. For example, the metal carboxylate salt is aluminum tristearate (CH 3 (CH 2) 16 COO) 3 Al, aluminum distearate (CH 3 (CH 2) 16 COO) 2 -Al-OH, and / or monostearate aluminum CH 3 (CH 2) 16 COO -Al (OH) 2 can contain. Other examples of metal carboxylate salts include titanium stearate, tin stearate, calcium stearate, zinc stearate, boron stearate and strontium stearate.

  The extracted metal carboxylate can be used as part of the catalyst composition and / or can be introduced directly into the reactor independently of the catalyst composition. For example, the extracted metal carboxylate salt and catalyst composition can be fed separately to the reactor.

  The amount of extracted metal carboxylate salt added to the reactor system depends on the catalyst system used, reactor preconditioning (reactor wall coating to control charging) and other factors well known to those skilled in the art. However, it can depend on, for example, reactor conditions, temperature and pressure, type of mixing device, amount of components to be combined, and even the mechanism by which the catalyst / continuous additive combination is introduced into the reactor. In certain embodiments, the ratio of the amount of extracted metal carboxylate salt in the reactor at a given time to the amount of polymer produced ranges from about 0.5 ppm to about 1000 ppm, or from about 1 ppm to about It can be in the range of 400 ppm, or in the range of about 5 ppm to about 50 ppm.

  The extracted metal carboxylate salt can be fed to the polymerization reactor as a solution or as a slurry. For example, the extracted metal carboxylate salt can be first mixed or combined with mineral oil to form a slurry that can be fed to the reactor.

  The extracted metal carboxylate salt and catalyst composition can be injected together into the reactor. For example, the catalyst can be in the form of an unsupported liquid, as described in US Pat. Nos. 5,31,036 and 5,693,727 and European Patent Publication No. 0593830A. The catalyst in liquid form can be fed to the reactor together with the extracted metal carboxylate using, for example, the injection method described in WO 97/46599.

  In certain embodiments, a catalyst compound can be contacted with an extracted metal carboxylate salt to make a catalyst composition. Contacting can also refer to bringing together, blending, mixing and the like.

  The extracted metal carboxylate salt can be present in the catalyst composition from about 0.1 to about 25 weight percent. Within this range, the extracted metal carboxylate salt is 0.5% or more, or 1% or more, or 2% or more, or 3% or more, or 4% or more, based on the total weight of the catalyst composition, or 5% or more, or 6% or more, or 7% or more, or 8% or more, or 9% or more, or 10% or more can be present in the catalyst composition. Within this range, the extracted metal carboxylate salt should be present in the catalyst composition in an amount of 20% or less, or 15% or less, or 10% or less, based on the total weight of the catalyst composition. Can do.

  In certain embodiments, a metallocene catalyst (and optionally another catalyst) is combined, contacted, blended, and / or mixed with the extracted metal carboxylate salt. The catalyst can be supported. Embodiments can include forming a catalyst, for example, forming a supported catalyst, and contacting the catalyst with an extracted metal carboxylate salt. In certain embodiments, the supported catalyst can be formed by incipient wetness impregnation or another technique for depositing the catalyst compound on the support.

  In certain embodiments, the supported metallocene catalyst is mixed with and / or substantially in contact with a significant portion of the supported catalyst with the extracted metal carboxylate salt along with the extracted metal carboxylate salt. Tumble for a long time. It is also possible to premix the extracted metal carboxylate salt with a co-catalyst or activator (eg, an organometallic compound such as methylalumoxane or modified methylalumoxane) prior to introduction into the reactor.

  In certain embodiments, the catalyst composition is supported and can be substantially dried, preformed and / or free flowing (free flowing). The preformed supported catalyst composition is contacted with the extracted metal carboxylate salt. The extracted metal carboxylate salt can be in the form of a solution, emulsion or slurry. It may also be in the form of a solid such as a free flowing powder. In another embodiment, the extracted metal carboxylate salt and a supported catalyst composition, such as a supported metallocene catalyst composition, in a rotary mixer such as a tumble mixer under a nitrogen atmosphere or in a fluidized bed. Contact in a mixing process.

  In certain embodiments, a metallocene catalyst is contacted with a support to form a supported catalyst compound. The activator for the catalyst compound can be contacted with another carrier to form a supported activator. The extracted metal carboxylate salt and the supported catalyst compound or supported activator can then be mixed in any order, can be mixed separately, mixed simultaneously, or supported. It can be mixed with only one of the catalysts or, for example, the separately supported catalyst prior to mixing the separately loaded catalyst and the active agent.

  The mixing and contacting technique can involve any mechanical mixing means such as shaking, stirring, tumbling and rolling. Another contemplated technique involves the use of fluidization, for example, the use of fluidization in a fluidized bed reactor in which the circulating gas is brought into contact.

Additional continuity additive / auxiliary In addition to the extracted metal carboxylate salt described above, one or more additional continuity additives are used, for example, to help control the static level in the reactor. It may be desirable. As used herein, the terms “continuous additive or auxiliary” and “anti-fouling agent” refer to compounds or compounds useful for reducing or eliminating reactor fouling in gas phase or slurry phase polymerization processes. Of a mixture (eg solid or liquid). Here, fouling is manifested by any number of phenomena including reactor wall sheeting, clogging of inlet and outlet tubes, formation of large agglomerates, or other forms of reactor malfunction well known to those skilled in the art. Can be done. In the present invention, these terms can be used interchangeably. The continuity additive can be used as part of the catalyst composition or can be introduced directly into the reactor independently of the catalyst composition. In certain embodiments, the continuity additive is supported on the inorganic oxide of the supported catalyst composition described herein.

  Non-limiting examples of continuous additives include fatty acid amines, amide-hydrocarbons or ethoxylated amide compounds such as those described as “surface modifiers” in WO 96/11961; carboxylate compounds such as There are aryl carboxylates and long chain hydrocarbon carboxylates and fatty acid-metal complexes; alcohols, ethers, sulfate compounds, metal oxides and other compounds well known in the art. Some specific examples of continuous additives include 1,2-diether organic compounds, magnesium oxide, ARMOSTAT 310, ATMER 163, ATMER AS-990, and other glycerol esters, ethoxylated amines (eg, N, N-bis (2-hydroxyethyl) octadecylamine), alkyl sulfonates, and alkoxylated fatty acid esters; STADIS 450 and 425, KEROSTAT CE 4009 and KEROSTAT CE 5009, chromium N-oleyl anthranilate salt, di-t-butylphenol and Calcium salt of Medialan acid; POLYFLO 130, TOLAD 511 (α-olefin-acrylonitrile copolymer and polymeric polyamine), EDENOL D32, sorbitan monooleate, glycerol monostearate, methyl toluate, dimethyl maleate, dimethyl fumarate, triethylamine 3,3-diphenyl-3 There are-(imidazol-1-yl) propynes and similar compounds. In certain embodiments, the additional continuity additive is the described carboxylate metal compound (optionally with other compounds described in this section).

  Any of the additional continuity additives described above can be used as the additional continuity additive, alone or in combination. For example, combining an extracted metal carboxylate salt with an amine-containing regulator {eg, extracted metal carboxylate salt is available from KEMAMINE (available from Chemtura Corporation) or ATMER (available from ICI Americas Inc.) Can be combined with any kind of product to which it belongs. For example, the extracted metal carboxylate salt can be added to an antistatic agent such as an aliphatic amine such as KEMAMINE AS 990/2 zinc additive, a blend of ethoxylated stearylamine and zinc stearate, or KEMAMINE AS 990/3, ethoxylated. It can be combined with a blend of stearylamine, zinc stearate and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate.

  Other additional continuity additives useful in the embodiments disclosed herein are well known to those skilled in the art. Regardless of which additional continuity additive is used, care should be taken in selecting the appropriate additional continuity additive so that no poison is introduced into the reactor. Further, in selected embodiments, additional continuity additives should be used in the minimum amount necessary to orient the static electricity in the desired range.

  The additional continuity additive is added to the reactor as a combination with two or more additional continuity additives listed above, or as a combination of the additional continuity additive and the extracted carboxylate metal salt. Can be added. Additional continuity additives can be added to the reactor in the form of a solution or slurry (eg, a slurry with mineral oil), can be added to the reactor as a separate feed stream, and other It can also be combined with the supply. For example, the additional continuous additive and catalyst or catalyst slurry can be combined prior to feeding the combined catalyst-static modifier mixture to the reactor.

  In certain embodiments, the additional continuous additive is added to the reactor in an amount ranging from about 0.05 to about 200 ppmw, or from about 2 to about 100 ppmw, or from about 2 to about 50 ppmw, based on the polymer production rate. Can be added to. In certain embodiments, the additional continuity additive can be added to the reactor in an amount of about 2 ppmw or more based on the polymer production rate.

Metallocene Catalyst The catalyst composition can include at least one metallocene catalyst component. As used herein, the term “catalyst composition” refers to a catalyst, such as a metallocene catalyst as described herein, at least one promoter (sometimes also referred to as an activator), and optional components (supports). , Additives, continuity additives / adjuvants, scavengers, etc.).

  The metallocene catalyst or metallocene component comprises one or more Cp ligands (cyclopentadienyl ligand and cyclopentadienyl-like ligand) that are bound to at least one Group 3-12 metal atom and at least one “Half-sandwich” compounds (ie, at least one ligand) and “full sandwich” compounds (ie, at least two ligands) having one or more leaving groups attached to the metal atom can be included. Hereinafter, these compounds are referred to as “metallocene” or “metallocene catalyst component”.

The one or more metallocene catalyst components are represented by the following formula (I).
Cp A Cp B MX n (I)

  The metal atom “M” of the metallocene catalyst compound as described throughout the specification and claims may in one embodiment be selected from the group consisting of Group 3-12 atoms and lanthanide series atoms. In a more specific embodiment it can be selected from the group consisting of Group 4, 5 and 6 atoms, in a more specific embodiment it can be selected from Ti, Zr, Hf atoms, In a more specific embodiment, it can be Zr. Unless otherwise indicated, the group attached to the metal atom “M” is such that the compounds described below in formulas and structures are neutral. The Cp ligand forms at least one chemical bond with the metal atom M to form a “metallocene catalyst compound”. Cp ligands differ from leaving groups attached to catalyst compounds in that they are less susceptible to substitution / extraction reactions.

  In certain embodiments, M is as described above; each X is chemically bonded to M; each Cp group is chemically bonded to M; n is an integer from 0 or 1-4; In form, it is 1 or 2.

The ligands represented by Cp A and Cp B in the formula (I) may be the same or different, and are cyclopentadienyl ligands or cyclopentadienyl-like ligands, which are either Or both may contain heteroatoms and either or both of them may be substituted with the group R. In one embodiment, Cp A and Cp B are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives thereof.

Each Cp A and Cp B of formula (I) may independently be unsubstituted or optionally substituted by one or a combination of substituents R. Non-limiting examples of substituent R when used in structure (I) include hydrogen groups, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, Lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkylthio, arylthio, thoxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene Alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phos Ino, phosphine, amino, amine, cycloalkyl, acyl, aroyl, alkylthiol, dialkylamine, alkylamide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl- and dialkyl-carbamoyl, acyloxy, acylamino, aroylamino and combinations thereof Is included.

  Non-limiting examples of alkyl substituents R with respect to formula (I) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl and t-butylphenyl groups, etc. All isomers, including t-butyl, isopropyl and the like) are included. Other possible groups include substituted alkyls and aryls such as fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbyl substituted organometalloid groups (trimethylsilyl, trimethylgermyl, methyldiethylsilyl, etc. ); And halocarbyl-substituted organometalloid groups (including tris (trifluoromethyl) silyl, methylbis (difluoromethyl) silyl, bromomethyldimethylgermyl, etc.); and disubstituted boron groups (including dimethylboron, for example); and disubstituted Group 15 groups (including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine), Group 16 groups (methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethyl) Including Rusurufido) are included. Other substituents R include olefins such as (but not limited to) olefinically unsaturated substituents including vinyl terminated ligands, such as 3-butenyl, 2-propenyl, 5- Hexenyl and the like are included. In certain embodiments, at least two R groups (eg, two adjacent R groups) are joined to comprise carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, and combinations thereof. A ring structure having 3 to 30 atoms selected from the group is formed. A substituent R such as 1-butanyl may form a bond to the element M.

Each X in formula (I) is a halogen ion, hydride, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, Lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkylthio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkaryl, halide, haloalkyl, Haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine From the group consisting of amino, amine, cycloalkyl, acyl, aroyl, alkylthiol, dialkylamine, alkylamide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl- and dialkyl-carbamoyl, acyloxy, acylamino, aroylamino and combinations thereof, Independently selected. In certain embodiments, X is C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 6 -C 12 aryl, C 7 -C 20 alkyl aryl, C 1 -C 12 alkoxy, C 6 -C. It can be 16 aryloxy, C 7 -C 18 alkyl aryloxy, C 1 -C 12 fluoroalkyl, C 6 -C 12 fluoroaryl and C 1 -C 12 heteroatom-containing hydrocarbons and substituted derivatives thereof. In certain embodiments, X is hydride, halide ions, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 7 -C 18 alkylaryl, C 1 -C 6 alkoxy, C 6 -C 14 aryloxy C 7 -C 16 alkylaryloxy, C 1 -C 6 alkyl carboxylate, C 1 -C 6 fluorinated alkyl carboxylate, C 6 -C 12 aryl carboxylate, C 7 -C 18 alkyl aryl carboxylate, C 1 -C 6 fluoroalkyl, C 2 -C 6 selected from fluoro alkenyl and C 7 -C 18 fluoroalkyl aryl; hydride in more specific embodiments still, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy , Tosyl, fluoromethyl and fluorophenyl. In certain embodiments, X is C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 6 -C 12 aryl, C 7 -C 20 alkyl aryl, substituted C 1 -C 12 alkyl, substituted C 6- C 12 aryl, may be selected from substituted C 7 -C 20 alkylaryl and C 1 -C 12 heteroatom-containing alkyl, C 1 -C 12 heteroatom-containing aryl, and C 1 -C 12 heteroatom-containing alkyl aryl. In certain embodiments, X is chloride, fluoride, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 7 -C 18 alkylaryl, halogenated C 1 -C 6 alkyl, halogenated C 2 -C Selected from 6 alkenyl and halogenated C 7 -C 18 alkylaryl. In certain embodiments, X is fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyl (mono-, di- and trifluoromethyl) and fluorophenyl (mono-, di- , Tri-, tetra- and pentafluorophenyl).

Examples of the metallocene catalyst compound and / or component include those in which Cp A and Cp B in the formula (I) are crosslinked with each other by at least one bridging group (A) to form a structure represented by the formula (II). The
Cp A (A) Cp B MX n (II)

These bridging compounds of the formula (II) are referred to as “bridged metallocenes”. Cp A , Cp B , M, X and n are as defined above for formula (I); where each Cp ligand is chemically bonded to M and (A) is chemically bonded to each Cp. Non-limiting examples of the bridging group (A) include divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent hetero Alkenyl, divalent alkynyl, divalent lower alkynyl, divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkylthio, divalent arylthio, divalent Aryl, divalent substituted aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl, divalent alkaryl, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent Valent heterocycle, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbyl, divalent lower hydrocarbon Building, divalent substituted hydrocarbyl, divalent heterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphino, divalent phosphine, divalent amino, divalent amine, divalent ether, divalent thioether encompassed. Additional non-limiting examples of bridging groups A include at least one Group 13-16 atom (such as, but not limited to, carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atoms and combinations thereof) Divalent hydrocarbon groups are included. Here, these heteroatoms may also be C 1 -C 12 alkyl or aryl substituted to meet neutral valence. The bridging group (A) may also contain substituents R as defined above (for formula (I)) including halogen groups and iron. Non-limiting examples more more specific bridging group (A) are, C 1 -C 6 alkylene, substituted C 1 -C 6 alkylene, oxygen, sulfur, R '2 C =, R ' 2 Si =, - Si (R ′) 2 Si (R ′ 2 ) —, R ′ 2 Ge =, R′P =, where “=” represents two chemical bonds, where R ′ is hydride, Independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl substituted organometalloid, halocarbyl substituted organometalloid, disubstituted boron, disubstituted group 15 atom, substituted group 16 atom and halogen group, 2 One or more R ′ may combine to form a ring or ring system. In one embodiment, the bridged metallocene catalyst component of formula (II) has two or more bridging groups (A).

  Other non-limiting examples of bridging groups (A) include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2, 2-tetramethylethylene, dimethylsilyl, diethylsilyl, methylethylsilyl, trifluoromethylbutylsilyl, bis (trifluoromethyl) silyl, di (n-butyl) silyl, di (n-propyl) silyl, di (isopropyl) Silyl, di (n-hexyl) silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di (t-butylphenyl) silyl, di (p-tolyl) silyl and Si atoms are Ge or C atoms The counterpart replaced by is included; dimethylsilyl Diethyl silyl, dimethyl germyl and diethyl germyl and the like.

  In another embodiment, the bridging group (A) may also be a ring containing, for example, 4-10 ring members, in a more specific embodiment 5-7 ring members. The ring members can be selected from the elements listed above from one or more of B, C, Si, Ge, N, and O in certain embodiments. Non-limiting examples of ring structures that can be present as or as part of a bridging moiety include cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and one or two Corresponding rings in which at least one of the carbon atoms is replaced by at least one of Si, Ge, N and O, in particular at least one of Si and Ge. The bond configuration between the ring and the Cp group may be cis, trans or combinations thereof.

  The cyclic bridging group (A) may be saturated or unsaturated and / or may have one or more substituents and / or one or more It may be condensed to other ring structures. When present, said one or more substituents are in one embodiment selected from the group consisting of hydrocarbyl (eg alkyl such as methyl) and halogen (eg F, Cl). Optionally, the one or more Cp groups that the above-mentioned cyclic bridging moieties may be condensed may be saturated or unsaturated, 4 to 10 ring members, more particularly 5, Selected from those having 6 or 7 ring members (in particular embodiments selected from the group consisting of C, N, O and S), such as cyclopentyl, cyclohexyl and phenyl. Furthermore, these ring structures may themselves be condensed, for example as in the case of naphthyl groups. In addition, these (optionally fused) ring structures may have one or more substituents. Illustrative non-limiting examples of these substituents include hydrocarbyl (especially alkyl) groups and halogen atoms.

The ligands Cp A and Cp B of formulas (I) and (II) are different from one another in one embodiment and the same in another embodiment.

  In still another aspect, the metallocene catalyst component includes a monoligand metallocene compound (for example, a monocyclopentadienyl catalyst component) as described in, for example, International Publication WO 93/08221 (incorporated herein by reference). Is included.

In yet another aspect, the at least one metallocene catalyst component is a non-bridged “half sandwich” metallocene represented by formula (III).
Cp A MQ q X n (III)

(Where Cp A is a ligand that is defined in the same way as for the Cp group in (I) and binds to M;
Each Q independently binds to M; Q also binds to Cp A in one embodiment;
X is a leaving group as described above in (I);
n is in the range of 0 to 3, in one embodiment 1 or 2;
q is in the range of 0-3, and in one embodiment is 1 or 2. )
In one embodiment, Cp A is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substitutions thereof, and combinations thereof.

In formula (III), Q is ROO-, RO-, R (O) -, - NR -, - CR 2 -, - S -, - NR 2, -CR 3, -SR, -SiR 3, -PR 2 , selected from the group consisting of —H and substituted and unsubstituted aryl groups, wherein R is hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl. , Substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkylthio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkenyl Reel, alkale , Halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, amine, cycloalkyl, acyl, aroyl, alkylthiol, dialkylamine, It is selected from the group consisting of alkylamide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl- and dialkyl-carbamoyl, acyloxy, acylamino, aroylamino and combinations thereof. In another aspect, R, C 1 -C 6 alkyl, C 6 -C 12 aryl, C 1 -C 6 alkylamine, C 6 -C 12 alkylaryl amines, C 1 -C 6 alkoxy, C 6 -C 12 Selected from the group consisting of aryloxy and the like. Non-limiting examples of Q include C 1 -C 12 carbamate, C 1 -C 12 carboxylate (eg pivalate), C 2 -C 20 allyl and C 2 -C 20 heteroallyl moieties.

In other words, the “half sandwich” metallocene can be described as in, for example, formula (II) as described in US Pat. No. 6,069,213.
Cp A M (Q 2 GZ) X n or T (Cp A M (Q 2 GZ) X n ) m (IV)

{Where M, Cp A , X and n are as defined above;
Q 2 GZ forms a multidentate ligand unit (eg, pivalate);
Wherein at least one of the Q groups forms a bond with M and each Q is independently selected from the group consisting of —O—, —NR—, —CR 2 — and —S—. Is;
G is carbon or silicon; and Z is selected from the group consisting of R, —OR, —NR 2 , —CR 3 , —SR, —SiR 3 , —PR 2 and hydride;
However, when Q is —NR—, Z is selected from the group consisting of —OR, —NR 2 , —SR, —SiR 3 , —PR 2 , and the neutral valence for Q depends on Z Satisfied;
Here, each R is hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl , Alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkylthio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkaryl, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl , Heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, amine, cycloalkyl Independently selected from the group consisting of: acyl, aroyl, alkylthiol, dialkylamine, alkylamide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl- and dialkyl-carbamoyl, acyloxy, acylamino, aroylamino, and combinations thereof; in the species of embodiments, R, C 1 -C 10 heteroatom-containing group, C 1 -C 10 alkyl, C 6 -C 12 aryl, C 6 -C 12 alkylaryl, C 1 -C 10 alkoxy and C 6 independently selected from the group consisting of -C 12 aryloxy;
n is 1 or 2,
T is a bridging group selected from the group consisting of C 1 -C 10 alkylene, C 6 -C 12 arylene, C 1 -C 10 heteroatom-containing group and C 6 -C 12 heterocyclic group, and each T group Is a bridge between adjacent “Cp A M (Q 2 GZ) X n ” groups, chemically bonded to the Cp A group,
m is an integer of 1 to 7, or an integer of 2 to 6. }

A as described above for (A) in structure (II) is in one embodiment a chemical bond, —O—, —S—, —SO 2 —, —NR—, = SiR 2 , = GeR 2, = SnR 2, -R 2 SiSiR 2 -, RP =, C 1 ~C 12 alkylene, substituted C 1 -C 12 alkylene, more divalent C 4 -C 12 cyclic hydrocarbons and substituted and unsubstituted aryl groups C 5 -C 8 cyclic hydrocarbon in specific embodiments more, -CH 2 CH 2 -, = is selected from CR 2 and = SiR 2 group consisting of; is selected from the group consisting of wherein, R represents 1 In one embodiment, it is selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, fluoroalkyl and heteroatom-containing hydrocarbons; in a more specific embodiment, R is C 1 -C 6 alkyl, substituted phenyl, phenyl And C 1 Selected from the group consisting of ˜C 6 alkoxy; in an even more specific embodiment, selected from the group consisting of methoxy, methyl, phenoxy and phenyl;
In yet another embodiment, A may not be present, in which case each R * is defined as for R 1 -R 13 ;
Each X is as described above in (I);
n is an integer 0-4, 1-3 in another embodiment, 1 or 2 in yet another embodiment;
R 1 to R 13 are independently a hydrogen group, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl. , Substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkylthio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl , Haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, amine Cycloalkyl, acyl, aroyl, alkyl thiols, dialkyl amine, alkyl amide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl - and dialkyl - carbamoyl, selected acyloxy, acylamino, from the group consisting aroylamino;
R 1 -R 13 are also independently in one embodiment C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 6 -C 12 aryl, C 7 -C 20 alkyl aryl, C 1- From the group consisting of C 12 alkoxy, C 1 -C 12 fluoroalkyl, C 6 -C 12 fluoroaryl, and C 1 -C 12 heteroatom-containing hydrocarbons and substituted derivatives thereof; in more specific embodiments, hydrogen groups , fluorine group, chlorine group, a bromine group, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 7 -C 18 alkylaryl, C 1 -C 6 fluoroalkyl, C 2 -C 6 fluoroalkenyl, C 7 is selected from the group consisting of -C 18 fluoroalkyl aryl; and in more specific embodiments more hydrogen group, a fluorine group, chlorine group, methyl, ethyl, propyl, isopropyl, butyl, isobutyl It can also be selected from the group consisting of t-butyl, hexyl, phenyl, 2,6-dimethylphenyl and 4-t-butylphenyl groups; adjacent R groups form saturated, partially saturated or fully saturated rings May be. )

  It is envisioned that the metallocene catalyst components described above include their structural isomers, optical isomers, enantiomers (racemic mixtures), and in one embodiment may be pure enantiomers.

  As used herein, a single bridged asymmetrically substituted metallocene catalyst component having a racemic and / or meso isomer is not considered per se as at least two different bridged metallocene catalyst components.

  The “metallocene catalyst compound” (also referred to herein as a “metallocene catalyst component”) can include any combination of any “embodiments” described herein.

  Other suitable metallocenes include, but are not limited to, U.S. Pat. Nos. 7,179,876, 7,169,864, 7,157,531, 7,129,302, 6,995,109, 6,958,306, US Pat. Nos. 6,884,748, 6,689,847, 6,309,997, 6,265,338, US Patent Application Publication Nos. 2007/0055028 and 2006/019925, and International Publications WO 97/22635, WO 00/699. / 22, WO01 / 30860, WO01 / 30861, WO02 / 46246, WO02 / 50088, WO04 / 026921, WO06 / 019494, and WO2010 / 039948 are included.

Conventional catalysts and mixed catalyst catalyst compositions can include one or more of the above metallocene catalysts and / or other conventional polyolefin catalysts and the following Group 15 atom-containing catalysts.

  A “Group 15 atom-containing” catalyst or “Group 15-containing” catalyst can comprise a complex of a Group 3 to Group 12 metal atom, wherein the metal atom is 2-8 coordinated. The coordination moiety can be at least 2 Group 15 atoms and up to 4 Group 15 atoms. For example, the Group 15-containing catalyst component is a complex of a Group 4 metal and 1-4 ligands, where the Group 4 metal is at least 2-coordinated and the coordination moiety is at least 2 nitrogens. Can be included. . Representative Group 15-containing compounds include, for example, International Publication No. WO99 / 01460; European Patent Publication No. 0893454A1; US Pat. No. 5,318,935; US Pat. No. 5,889,128, US Pat. No. 6,333,389B2, and This is disclosed in US Pat. No. 6,271,325 B1.

In one embodiment, the Group 15-containing catalyst comprises a Group 4 iminophenol complex, a Group 4 bis (amide) complex, and a Group 4 pyridylamide complex that are active to any degree to olefin polymerization. it can. In one possible embodiment, the Group 15-containing catalyst component is a bisamide such as [(2,3,4,5,6Me 5 C 6 ) NCH 2 CH 2 ] 2 NHZrBz 2 (obtained from Boulder Chemical). Compounds can be included.

Activators and activation methods for catalyst compounds Embodiments of the catalyst composition can further comprise an activator. As used herein, an “activator” is defined in a broad sense as any combination of substances that increase the rate at which a transition metal compound oligomerizes or polymerizes unsaturated monomers such as olefins.

  In certain embodiments, the activator is a Lewis base such as diethyl ether, dimethyl ether, ethanol or methanol. Other active agents that can be used include those described in WO 98/07515, such as tris (2,2 ′, 2 ″ -nonafluorobiphenyl) fluoroaluminate.

  A combination of activators may be used. For example, an alumoxane and an ionization activator can be used in combination. For example, see the specifications of European Patent Publication No. 0573120B1, International Publication Nos. WO94 / 07928 and WO95 / 14044, and US Pat. Nos. 5,153,157 and 5,453,410. International Publication WO 98/09996 describes the activation of metallocene catalyst compounds by perchlorates, periodates and iodates (including their hydrates). International publications WO 98/30602 and WO 98/30603 describe the use of lithium (2,2′-bisphenyl-ditrimethylsilicate) · 4THF as an activator for metallocene catalyst compounds. International Publication No. WO 99/18135 describes the use of organoboron-aluminum activators. European Patent Publication No. 0 721 299 B1 describes the use of a silylium salt in combination with a non-phase-compatible anion. International Publication No. WO 2007/024773 suggests the use of an activator-support that can include chemically treated solid oxides, clay minerals, silicate minerals or any combination thereof. In addition, activation methods using radiation (see European Patent Publication No. 0661581B1), electrochemical oxidation, etc. are also used to convert neutral metallocene catalyst compounds or precursors into metallocene cations capable of polymerizing olefins. Can be envisioned as a method Other activators and methods for activating metallocene catalyst compounds are described, for example, in US Pat. Nos. 5,849,852, 5,589,653 and 5,869,723, and in International Publication No. WO 98/32775.

  In certain embodiments, alumoxane can be used as an activator in the catalyst composition. Alumoxanes are generally oligomeric compounds containing —Al (R) —O— subunits, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. In particular, when the extractable ligand is a halide, an alkylalumoxane and a modified alkylalumoxane are suitable as the catalyst activator. Mixtures of various alumoxanes and modified alumoxanes can also be used. For further explanation, U.S. Pat. Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,920,418, 4,908,463. No. 4,968,827, No. 5,329,032, No. 5,248,801, No. 5,350,811, No. 5,157,137, No. 5103031, and European Patent Publication Nos. 0561476A1, No. 0279586B1, No. 0516476A. No. 5, 0594218A1 and International Publication No. WO94 / 10180.

  Alumoxanes can be produced by hydrolysis of the respective trialkylaluminum compounds. MMAO can be made by hydrolysis of trimethylaluminum and higher trialkylaluminum (eg, triisobutylaluminum). MMAO is generally more soluble in aliphatic solvents and is more storage stable. There are various methods for preparing alumoxanes and modified alumoxanes, non-limiting examples of which are U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4874734, 4924018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,350,811, 5,157,137, 5,103,301, 5,391,793, 5,391,529, 5,693,838, 5,573,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 And European Patents No. 0561476A, the No. 0279586B1, those described in Japanese, as well as International Patent Publication WO94 / 10180 and ibid WO99 / No. 15 534 of the same No. 0594218A item and the second 0586665B1. In one embodiment, a visually clear methylalumoxane can be used. The cloudy alumoxane or the gelled alumoxane can be made into a transparent solution by filtration, and the clear alumoxane can be decanted from the cloudy solution. Another alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A (disclosed in US Pat. No. 5,041,584, commercially available under the trade name Modified Methyl Alumoxane type 3A from Akzo Chemicals). is there

  In certain embodiments, neutral or ionic ionizing activators or stoichiometric activators such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, trisperfluorophenylboron metalloid precursors or A trisperfluoronaphthyl boron metalloid precursor, a polyhalogenated heteroborane anion (see eg WO 98/43983), boric acid (see eg US Pat. No. 5,942,459) or combinations thereof It may be used. Neutral or ionic activators may be used alone or in combination with alumoxane or modified alumoxane activators.

  Examples of neutral stoichiometric activators can include trisubstituted boron, tellurium, aluminum, gallium and indium or mixtures thereof. Each of the three substituents can be independently selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxy and halide. In embodiments, the three substituents can be independently selected from halogen, monocyclic or polycyclic (including halo-substituted) aryl, alkyl and alkenyl compounds and mixtures thereof; certain embodiments An alkenyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryl group having 3 to 20 carbon atoms ( Substituted aryl). Alternatively, these three groups are alkyl having 1 to 4 carbon atoms, phenyl, naphthyl, or mixtures thereof. In another embodiment, these three groups are halogenated (in one embodiment, fluorinated) aryl groups. In yet another exemplary embodiment, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronaphthyl boron.

  An ionic stoichiometric activator compound attaches an active proton or some other cation that is linked to the rest of the ion of the ionizing compound but is not coordinated or loosely coordinated to the ion. Can be contained. Such compounds and analogs are disclosed in, for example, European Patent Publication Nos. 0570982A, 0520732A, 0495375A, 0500754B1, 0277703A and 0277004A, and US Pat. No. 5,153,157, No. 5,198,401, No. 5,067,741, No. 5,206,197, No. 5,214,025, No. 5,384,299 and No. 5,502,124.

Catalyst Compound / Activator Loading Method The catalyst compound described above can be combined with one or more supports using one of the loading methods well known in the art or the loading methods described below. For example, the catalyst compound can be in a supported form, eg, deposited on, contacted with, incorporated into, or adsorbed or absorbed in or on the support.

  As used herein, the term “support” refers to compounds comprising Group 2, Group 3, Group 4, Group 5, Group 13 and Group 14 oxides and chlorides. Suitable carriers include, for example, silica, magnesia, titania, zirconia, montmorillonite, phyllosilicate, alumina, silica-alumina, silica-chromium, silica-titania, magnesium chloride, graphite, magnesia, titania, zirconia, montmorillonite, and phyllosilicate. Is included.

  The carrier can have an average particle size in the range of about 0.1 to about 50 μm, or about 1 to about 40 μm, or about 5 to about 40 μm.

  The support can have an average pore size in the range of about 10 to about 1000 inches, or about 50 to about 500 inches, or 75 to about 350 inches. In certain embodiments, the average pore size of the support is from about 1 to about 50 μm.

The support can have a surface area in the range of about 10 to about 700 m 2 / g, or about 50 to about 500 m 2 / g, or about 100 to about 400 m 2 / g.

  The carrier can have a pore volume ranging from about 0.1 to about 4.0 cc / g, or from about 0.5 to about 3.5 cc / g, or from about 0.8 to about 3.0 cc / g. .

  The carrier can have an average particle size in the range of about 1 to about 500 μm, or about 10 to about 200 μm, or about 5 to about 100 μm.

Supports such as inorganic oxides have a surface area in the range of about 10 to about 700 m 2 / g, a pore volume in the range of about 0.1 to about 4.0 cc / g, and an average particle size in the range of about 1 to about 500 μm. Can have. In another embodiment, the support has a surface area in the range of about 50 to about 500 m 2 / g, a pore volume in the range of about 0.5 to about 3.5 cc / g, and an average particle size in the range of about 10 to about 200 μm. be able to. In certain embodiments, the surface area of the support is about 100 to about 400 m 2 / g, and the support has a pore volume of about 0.8 to about 3.0 cc / g and an average particle size of about 5 to about 100 μm. Have

  Multiple catalyst compounds can be supported together with the activator on the same support or on separate supports, or the active agent can be used in an unsupported form or deposited on a separate support from the supported catalyst compound. It can also be made.

  There are a variety of alternative methods in the art for loading polymerization catalyst compounds. For example, the catalyst compound can contain a polymer-bound ligand as described, for example, in US Pat. Nos. 5,473,202 and 5,770,755; the catalyst is described, for example, in US Pat. No. 5,648,310. The support used with the catalyst can also be functionalized as described in EP 0802203A and at least one substituent or leaving group is Selected as described in US Pat. No. 5,688,880.

  In certain embodiments, initial wet impregnation can be used to combine the catalyst compound and one or more support materials. Initial wet impregnation can result in a catalyst composition with increased catalyst productivity as compared to other catalyst preparation techniques.

  Initial wet impregnation can include dissolving one or more components (eg, catalyst compound, activator, etc.) of the catalyst composition in a solvent. The volume of the mixture of one or more catalyst components can vary depending on, for example, the catalyst composition being produced. According to this embodiment, the mixture can be combined with the support in order to impregnate the support with one or more catalyst components. A particularly important factor in impregnation is the pore volume of the support. In particular, the volume of the mixture of one or more catalyst components should be sufficient to fill the pore volume of the support without forming a slurry of the mixture and support. In one embodiment, the volume of the mixture does not exceed about 120% of the pore volume of the carrier, or does not exceed about 110% of the pore volume of the carrier, or does not exceed about 105% of the pore volume of the carrier. And In certain embodiments, the volume of the mixture is substantially the same as the pore volume of the support.

  The solvent can then be removed from the impregnated pores of the support. For example, the solvent can be removed from the support by heating and / or vacuum. In certain embodiments, the positive pressure for the vacuum can be provided by an inert gas such as nitrogen. It should be understood that the heating of the impregnated support should be controlled to reduce and / or prevent unwanted agglomeration of the catalyst particles and / or crosslinking of the active agent that may be used.

  Solvents for use in the initial wet impregnation include, for example, solvents in which the metallocene catalyst and / or activator is at least partially soluble. Non-limiting examples of suitable solvents include aromatic hydrocarbons, halogenated aromatic hydrocarbons, ethers, cyclic ethers or esters. Specific examples of suitable solvents include THF (tetrahydrofuran), dichloromethane, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, diethyl ether, di-n-butyl ether, 1,4-dioxane and combinations thereof. Can be included.

Polymerization Process Embodiments of the polymerization process can include polymerization of olefins in the presence of a metallocene catalyst compound and an extracted metal carboxylate salt. Polymerization methods can include solution, gas phase, slurry phase and high pressure methods or combinations thereof. In an exemplary embodiment, gas phase or slurry phase polymerization of one or more olefins, at least one of which is ethylene or propylene, is provided.

  The catalysts and catalyst compositions described above may be suitable for use in any prepolymerization and / or polymerization process over a wide range of temperatures and pressures. The temperature ranges from about 60 ° C to about 280 ° C, or from 50 ° C to about 200 ° C, or from about 60 ° C to about 120 ° C, or from about 70 ° C to about 100 ° C, or from about 80 ° C to about The desired temperature range can include any combination of any upper limit and any lower limit described herein.

  The one or more olefin monomers used in this polymerization method can have 2 to 30 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms. For example, this polymerization method can include two or more olefins or comonomers such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and the like. Can be used.

  Copolymers of ethylene can be produced in this polymerization process, where ethylene is an α-olefin comonomer having 4 to 15 carbon atoms, or 4 to 12 carbon atoms, or 4 to 8 carbon atoms. And polymerize.

  Typically, in a gas phase polymerization process, a recycle gas stream (also referred to as a recycle stream or fluidizing medium) is heated in the reactor by the heat of polymerization in some part of the cycle of the reactor system. A cycle is adopted. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor. In general, in a gas phase fluidized bed process for producing a polymer, a gas stream containing one or more monomers is continuously circulated through the fluidized bed in the presence of a catalyst under reactive conditions. This gas stream is removed from the fluidized bed and recycled back to the reactor. At the same time, the polymer product is removed from the reactor and new monomer is added instead of polymerized monomer. (For example, U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,31,636, 5,535,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, (See the specifications of US Pat. Nos. 5,616,661 and 5,668,228)

  The reactor pressure in the gas phase process is, for example, from about atmospheric to about 600 psig (4138 kPa), or from about 100 psig (690 kPa) to about 500 psig (3448 kPa), or from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), or about 250 psig ( 1724 kPa) to about 350 psig (2414 kPa).

  The reactor temperature in the gas phase process can range from about 30 ° C to about 120 ° C, or from about 60 ° C to about 115 ° C, or from about 70 ° C to 110 ° C, or from about 70 ° C to about 95 ° C.

  Other gas phase processes contemplated include U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375 and European Patent Publication Nos. 0794200A, 0802202A, 0891990A2 and What is described in each publication of 634421B is also included.

  In slurry polymerization processes, pressures in the range of about 1 to about 50 atmospheres and higher and temperatures in the range of 0 ° C. to about 120 ° C. are generally employed. In the slurry polymerization process, a suspension of solid particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomer and often hydrogen are added along with the catalyst. This suspension containing the diluent is withdrawn from the reactor intermittently or continuously and the volatile components are separated from the polymer and recycled (optionally after distillation) to the reactor. The liquid diluent used in the polymerization medium is typically an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The medium used should be liquid and relatively inert under the polymerization conditions. If a propane medium is used, the process must be operated above the critical temperature and pressure of the reaction diluent. In one embodiment, hexane or isobutane media is used. Examples of solution and slurry phase polymerization methods are those described in U.S. Pat. Nos. 3,248,179, 4,613,484, 4,271,060, 5001,205, 5,236,998 and 5,589,555. Is included.

Polymer Products The polymers produced by the methods described herein can be used in a wide variety of products and end uses. The polymers produced include, but are not limited to, linear low density polyethylene, low density polyethylene and high density polyethylene.

These polymers range from about 0.86 g / cm 3 to about 0.97 g / cm 3 , or from about 0.88 g / cm 3 to about 0.965 g / cm 3 , or from about 0.900 g / cm 3 to It can have a density in the range of about 0.96 g / cm 3 .

The polymer has a weight average molecular weight to number average molecular weight ratio (M w / M n ) of, for example, greater than 1.5 to about 15, in particular greater than 2 to about 10, even more preferably greater than about 2.2 to less than about 8. It can have a certain molecular weight distribution.

The polymer may be in the range of 0.01 dg / min to 1000 dg / min, as measured by ASTM method D-1238-E (190 / 2.16), or in the range of about 0.01 dg / min to about 100 dg / min, or It can have a melt index (MI) or (I 2 ) in the range of about 0.1 dg / min to about 100 dg / min.

The polymer may have a melt index ratio (I 21 / I 2 ) in the range of 5 to 300 in, or less than about 10 to 250, or 15 to 200, or 20 to 180, where I 21 is ASTM method D-1238-F. [190 / 21.6]).

  Polymers produced by the methods disclosed herein and blends of such polymers with other polymers are used in molding operations such as film, pipe, sheet and fiber extrusion and coextrusion as well as blow molding, injection molding and rotational molding. Can be useful.

  The following examples are intended to provide those skilled in the art with a complete disclosure and explanation of how to make and use the compounds of the present invention and are intended to limit the scope of what the inventors regard as inventions. Not what you want.

  In the examples, the following catalyst compounds and continuity additives were used.

Continuity additive 1
Continuous additive 1 (“CA-1”) was a mixture of hydroxyethyl stearylamine (25-50 wt%) and a metal carboxylate salt (50-75 wt%). The metal carboxylate salt was aluminum stearate available from Chemtura Corporation, Memphis, Tennessee. The aluminum stearate had an ash content of about 11-12%, a water content of about 0.5%, and a free fatty acid content of about 3-4%. CA-1 was used as a slurry in mineral oil.

Continuity additive 2
Continuous additive 2 (“CA-2”) was a metal carboxylate salt prepared by extraction with acetone. Aluminum stearate was extracted with acetone by combining aluminum stearate and acetone with stirring. Acetone had a dielectric constant of 20.70 measured at 25 ° C. The weight ratio of acetone to aluminum stearate was about 6: 1. After combining, the acetone was then removed and the extracted aluminum stearate was dried, sieved and weighed to determine the amount of material removed by extraction. In this extraction, 3-4% by weight of solubles were removed by extraction. CA-2 was used as a slurry in mineral oil.

Continuity additive 3
Continuous additive 3 (“CA-3”) was a metal carboxylate salt prepared by extraction with methanol. Aluminum stearate was extracted with methanol by combining aluminum stearate and methanol with stirring. Methanol had a dielectric constant of 32.63 at 25 ° C. The weight ratio of methanol to aluminum stearate was about 6: 1. After being combined, the methanol was then removed and the extracted aluminum stearate was dried, sieved and weighed to determine the amount of material removed by extraction. In this extraction, 4-6% by weight of solubles were removed by extraction. CA-3 was used as a slurry in mineral oil.

Catalyst A
The metallocene catalyst compound in Catalyst A was bis (n-propyl-cyclopentadienyl) hafnium dimethyl ((n-propylCp) 2 HfMe 2 ) metallocene available from Boulder Scientific Company, USA. The catalyst compound was supported on ES757 grade silica having a loss on ignition (LOI) of about 0.4 wt% water dehydrated at 875 ° C. in air. LOI is measured by measuring the weight loss of a support material heated to a temperature of about 1000 ° C. and held for about 22 hours. ES757 silica has an average particle size of 25 microns and is available from PQ Corporation.

The first step in the production of the above metallocene-type catalyst involves forming a precursor solution. 2.2 pounds (1 kg) of sparged and dried toluene was added to the stirred reactor, followed by 2.34 pounds (1.06 kg) of 30 wt% methylaluminoxane (MAO) in toluene (Baton Rouge, Louisiana, USA). Available from Albemarle, Inc.). The reactor was charged with 0.205 lb (93 g) of a 24.7 wt% toluene solution of (n-propyl Cp) 2 HfMe 2 catalyst compound and an additional 0.22 lb (0.1 kg) of toluene. The precursor solution is then stirred at 21.1 ° C. for 1 hour.

  While stirring the precursor solution, 1.87 pounds (0.85 kg) of 875 ° C. dehydrated silica support was slowly added to the precursor solution and the mixture was stirred at 21.1 ° C. The reactor contents are then mixed for 60 minutes while heating to 75 ° C. A vacuum was then applied and the polymerization catalyst mixture was dried to a free flowing powder. The final polymerization catalyst weighed 2.65 pounds (1.2 kg) and had a Zr weight percent of 0.8 and an Al weight percent of 12.0.

Catalyst B
Catalyst B was a cross-linked bulky (bulky) ligand metallocene catalyst compound formulated with aluminum stearate as part of the catalyst composition. The bridged bulky ligand metallocene-type catalyst compound used was dimethylsilylbis (tetrahydroindenyl) zirconium dichloride (Me 2 Si (H 4 Ind) 2 ZrCl 2 ) metallocene available from Albemarle Corporation, Baton Rouge, Louisiana. was. The Me 2 Si (H 4 Ind) 2 ZrCl 2 catalyst compound was supported on Crosfield ES-70 grade silica with a loss on ignition (LOI) of about 1.0 wt% water dehydrated at 600 ° C. The LOI was measured by measuring the weight loss of the support material heated to a temperature of about 1000 ° C. and held for about 22 hours. Crosfield ES-70 grade silica has an average particle size of 40 microns and is available from Crosfield Limited, Warrington, England.

The first step in the production of the supported bulky ligand metallocene-type catalyst described above involves forming a precursor solution. 460 pounds (209 kg) of sparged and dried toluene is added to the stirred reactor, followed by 1060 pounds (482 kg) of 30 wt% methylaluminoxane (MAO) in toluene (obtained from Albemarle, Baton Rouge, Louisiana, USA) Possible). The reactor was charged with 947 pounds (430 g) of a 2 wt% toluene solution of Me 2 Si (H 4 Ind) 2 ZrCl 2 catalyst compound and an additional 600 pounds of toluene (272 kg). The precursor solution is then stirred at 80-100 ° F. (26.7-37.8 ° C.) for 1 hour.

While stirring the precursor solution, 850 pounds (386 kg) of 600 ° C. Crosfield dehydrated silica support is slowly added to the precursor solution and the mixture is added at 80-100 ° F. (26.7-37.8 ° C.) for 30 minutes. Stir. At the end of the mixture stirred for 30 min, available from Witco Corporation of USA Memphis, TN located as Kemamine AS-990 N, N- bis (2-hydroxyethyl) octadecylamine ((C 18 H 37 N ( CH 2 CH 240 lb (109 kg) of a 10 wt% toluene solution of 2 OH) 2 ) is added along with an additional 110 lb (50 kg) of toluene rinse, and the reactor contents are then heated to 175 ° F. (79 ° C.). 30 minutes later, a vacuum was applied and the polymerization catalyst mixture was dried at 175 ° F. (79 ° C.) for about 15 hours to a free-flowing powder with a final polymerization catalyst weight of 1200 lbs. (544 kg) with a Zr weight percent of 0.35 and an Al weight percent of 12.0.

Catalyst C
A 1 kg sample of Catalyst B prepared as described above was metered into a 3 liter glass flask under an inert atmosphere. 40 g CA-1 was dried under vacuum at 85 ° C., added to the flask and the contents tumbled / mixed for 20 minutes at room temperature. CA-1 appeared to be uniformly dispersed throughout the catalyst particles.

Catalyst D
Catalyst D was a blend of a bulky (bulky) ligand metallocene-type catalyst compound with aluminum stearate extracted as part of the catalyst composition. A 1 kg sample of Catalyst B prepared as described above was metered into a 3 liter glass flask under an inert atmosphere. 40 g of CA-2 prepared as described above was dried at 85 ° C. under vacuum, added to the flask and the contents tumbled / mixed at room temperature for 20 minutes. CA-2 appeared to be uniformly dispersed throughout the catalyst particles.

Catalyst E
The metallocene catalyst compound used for catalyst E is bis (n-propyl-cyclopentadienyl) hafnium dimethyl available from Boulder Scientific Company, USA. The catalyst compound is deposited on the support using initial wet impregnation. The catalyst compound is supported on ES757 grade silica dehydrated at 875 ° C. ES757 grade silica has an average particle size of 25 microns and is available from PQ Corporation.

  The first step in the production of the above metallocene-type catalyst involves forming a precursor solution. In a nitrogen dry box, 0.24 pounds (10.88 g) of bis (n-propyl-cyclopentadienyl) hafnium dimethyl was added to a solution of 30 wt% methylaluminoxane (MAO) in toluene. This precursor solution was then stirred at ambient temperature for 1 hour. Next, 0.882 pounds (400 g) of ES757 silica dehydrated at 875 ° C. was poured into a stainless steel mixing bowl from KitchenAid Blender. A wire whisk was attached and the silica was stirred at the lowest setting. The above precursor solution was slowly added to the silica over 45 minutes while stirring the silica. After the addition, the catalyst mixture was stirred for an additional hour at ambient temperature. The catalyst mixture was then divided into two 500 milliliter pear flasks. These flasks were attached to a rotary evaporator and the catalyst was dried at 70 ° C. under vacuum.

Catalyst F
The metallocene catalyst compound used for catalyst F is bis (n-propyl-cyclopentadienyl) hafnium dimethyl available from Boulder Scientific Company, USA. The catalyst compound is deposited on the support using initial wet impregnation. This metallocene-type catalyst was prepared using a procedure similar to that described above for Catalyst E, except that the catalyst compound was not deposited on ES757 silica, but dehydrated at 600 ° C. for 948 grade silica. Attached on top. This 948 grade silica has an average particle size of 55 microns and is available from WR Grace, USA.

Example 1
The following example relates to a gas phase polymerization process carried out with ethylene and hexane comonomer in a pilot plant fluidized bed reactor. This reactor was used to evaluate the use of extracted metal carboxylate salts as continuity additives. Table 1 shows three different tests, with reported reaction conditions for each test. Catalyst productivity is also reported in Table 1. Table 2 shows various properties of the resulting product, including resin bulk density.

  The polymerization was carried out in a continuous gas phase fluidized bed reactor. Each test was operated using the same continuous gas phase fluidization reactor. The fluidized bed consisted of polymer particles. Gas feed streams of hydrogen and ethylene combined with liquid comonomer were mixed together in a mixing T configuration and introduced into the recycle gas line under the reactor bed. A monomer group of 1-hexene was used as a comonomer. The individual flow rates of ethylene, hydrogen and comonomer were adjusted to maintain a constant composition target, as shown in Table 1 below. The ethylene concentration was adjusted to maintain a constant ethylene partial pressure. Hydrogen was adjusted to maintain a constant hydrogen to ethylene molar ratio. All gas concentrations were measured by on-line gas chromatography to have a relatively constant composition in the recycle gas stream.

  Catalyst A was injected directly into the fluidized bed using purified nitrogen as a carrier. The speed was adjusted to maintain a constant production rate. The continuous additive was injected separately from catalyst A directly into the fluidized bed using purified nitrogen as a carrier. The rate of continuity additive was adjusted to maintain a constant continuity additive to product ratio. The reacting bed of growing polymer particles was kept in a fluid state by continuously flowing replenishment and recycle gas through the reaction zone. To achieve this, an apparent gas velocity of 1-3 feet / second (0.3-0.9 m / second) was used. The reactor was operated at a total pressure of 300 psig (2070 kPa). In order to maintain a constant reaction temperature, the temperature of the recycle gas was continuously increased and decreased to accommodate changes in the rate of heat generation due to polymerization.

  The fluidized bed was kept at a constant height by removing a portion of the bed at a rate equal to the rate of formation of the granular product. The product was taken semi-continuously through a series of valves into a constant volume chamber, which was simultaneously evacuated back to the reactor. This allows much unreacted gas to be recycled back to the reactor at that time, allowing very efficient product removal. The product was purged to remove entrained hydrocarbons and treated with a damp nitrogen stream to deactivate traces of residual catalyst.

Table 1 below gives the polymerization parameters for Example 1. The catalyst productivity for each test is also given in Table 1.

  As shown in Table 1 above, Catalyst A using 30 ppm of CA-1 gave a productivity of 10988 g / g, and the catalyst productivity increased to 11423 g / g when 30 ppm of CA-2 was used in Test 3. . In Test 2, the catalyst productivity was further increased to 13794 g / g when the CA-2 loading was reduced to 15 ppm.

The properties of the resin produced in each test of Example 1 were measured by the following method:
1. Melt index (I 2 ): ASTM method D-1238-04C, 190 ° C., 2.16 kg;
2. High load melt index (I 21 ): ASTM method D-1238-04C, 190 ° C., 21.6 kg;
3. Density: ASTM method D-105; Bulk density: Pour the resin from a 7/8 inch diameter funnel into a 400 cc constant volume cylinder. The bulk density is determined as the value given in g / cc by dividing the weight of the resin by 400 cc.

Table 2 below gives the properties of the resin produced in Example 1.

Example 2
To evaluate the use of the extracted metal carboxylate salt as a continuous additive, an additional gas phase polymerization was carried out in the pilot plant fluidized bed reactor from Example 1. Table 3 shows four different tests, with reported reaction conditions for each test. Catalyst productivity is also reported in Table 3. Table 4 shows various properties of the resulting polymer product, including resin bulk density.

  The polymerization procedure for testing the aluminum stearate extracted for Example 2 is the same as that used and described above in Example 1. In Example 2, four tests were performed using a continuous gas phase fluidized bed reactor. In Test 4, Catalyst C was used with CA-1 as a continuity additive. In Test 5, Catalyst D was used with CA-1 as a continuity additive. In Test 6, Catalyst D was used with CA-2 as a continuity additive. In Test 7, Catalyst C was used with CA-3 as a continuity additive.

Table 3 below gives the polymerization parameters for Example 2. The catalyst productivity for each test is also given in Table 3.

  As shown in Table 3 above, Catalyst C using CA-1 in Test 4 gave a productivity of 6875 g / g. For test 5, catalyst productivity increased to 7592 g / g when catalyst D formulated with CA-2 was added to the reactor using the same concentration of CA-1. The highest productivity was observed for test 6 in which the catalyst was blended with extracted CA-2 and CA-2 was also added directly to the reactor as a continuity additive. In particular, Catalyst D using CA-2 gave a productivity of 7688 g / g in Test 6. Therefore, this data shows that the catalyst productivity increased when used by introducing the extracted aluminum stearate as part of the catalyst composition or directly into the reactor independently of the catalyst composition. And shows that the largest increase was observed when extracted aluminum stearate was used in the catalyst composition and introduced independently into the reactor.

The properties of the resin produced in each test were measured using the test method described above for the resin produced in Example 1. Table 4 below gives the properties of the resin produced in Example 2.

  As shown in Table 4 above, the extraction of aluminum stearate also provided increased resin standing bulk density. In particular, the resin produced from Test 4 using Catalyst C and CA-1 had a bulk density of 0.4713 g / cc. However, increased bulk density was observed for tests 5-7. In particular, in Test 5 where the catalyst was blended with extracted aluminum stearate (CA-2), a bulk density of 0.4760 g / cc was observed. An increased bulk density (0.4743 g / cc) was also observed for Test 7 using extracted aluminum stearate (CA-3) as a continuity additive. However, for Test 6 where the extracted aluminum stearate (CA-2) was used in the catalyst composition and introduced independently into the reactor, the largest increase in bulk density was observed. As shown in Table 4, the bulk density for Test 6 was 0.4818 g / cc.

Example 3
The following example relates to a gas phase polymerization carried out in a pilot plant fluidized bed reactor using ethylene and hexene comonomer to evaluate the use of a metallocene catalyst compound prepared by initial wet impregnation. Table 5 shows two different tests, with reported reaction conditions for each test. Catalyst productivity is also reported in Table 5. Table 6 shows the various properties of the resulting product, including the resin bulk density.

  The polymerization procedure for test catalysts E and F produced using initial wet impregnation is the same as described and used above in Example 1. In Example 3, two tests were performed using a continuous gas phase fluidized bed reactor. In test 8, catalyst E was used, and in test 9, catalyst F was used. In Test 8 and Test 9, CA-1 was used.

Table 5 below gives the polymerization parameters for Example 3. The catalyst productivity for each test is also given in Table 5.

  As shown in Table 5 above, Catalysts E and F prepared as described above by initial wet impregnation resulted in increased catalyst productivity compared to Test 1 from Example 1. . In Test 1, Catalyst A was used without using the initial wet impregnation. In particular, Catalyst A only gave a productivity of 10988 g / g in Test 1 whereas Catalyst E gave a productivity of 14974 g / g in Test 8 and Catalyst F produced 11507 in Test 9 Gave sex. Thus, this data shows that catalyst productivity can be increased when the catalyst composition is deposited on the support using initial wet impregnation.

The properties of the resin produced in each test of Example 3 were measured using the test methods described above for the resin produced in Example 1. Table 6 below gives the properties of the resin produced in Example 3.

  Only specific ranges are explicitly disclosed here, but ranges from any lower limit can be combined with any upper limit to express ranges not explicitly stated, and are explicitly stated A range from any lower limit can be combined with any other lower limit to illustrate a range that is not explicitly described, as well as from any upper limit to account for a range not explicitly stated The range can be combined with any other upper limit.

  Although the present invention has been described in terms of numerous embodiments and examples, those skilled in the art can devise other embodiments after reading this disclosure without departing from the scope and spirit of the invention disclosed herein. You will understand. Although individual embodiments are discussed, the invention covers all combinations of all these embodiments.

All references cited herein are incorporated by reference for all jurisdictions that permit their incorporation to the extent that their disclosure is consistent with the description of the invention.
In addition, although this application is related with the invention as described in a claim, the following can also be included as another aspect.
(1) a polymerization process comprising polymerizing an olefin in the presence of a catalyst composition and an extracted metal carboxylate salt in a reactor,
The process as described above, wherein the extracted metal carboxylate salt is obtained by extracting the metal carboxylate salt with an organic solvent having a dielectric constant at 25 ° C. of 3.0 or higher.
(2) The method according to (1) above, wherein the extracted metal carboxylate salt contains essentially no free carboxylic acid.
(3) The method according to (1) or (2) above, wherein the extracted metal carboxylate salt contains less than 1% by weight of total free acid based on the total weight of the extracted metal carboxylate salt. .
(4) The organic solvent is C1-C10 alcohol, C1-C10 ketone, C1-C10 ester, C1-C10 ether, C1-C10 alkyl halide, C1-C10 alkylonitrile, C1-C10 dialkyl sulfoxide and combinations thereof. The method according to any one of (1) to (3) above, which is selected from the group consisting of:
(5) The organic solvent is methanol, ethanol, propanol, isopropanol, butanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, methyl propionate, methyl butyrate, dimethyl ether, diethyl ether, 1,4-dioxane, tetrahydrofuran, chloroform, dichloromethane The method in any one of said (1)-(4) selected from acetonitrile, dimethylsulfoxide, and those combination.
(6) The metal carboxylate salt has the following formula:
MQx (OOCR) y
(Where M is a Group 13 metal from the Periodic Table of Elements;
Q is a halogen, hydroxy, alkyl, alkoxy, aryloxy, siloxy, silane or sulfonate group;
R is a hydrocarbyl group having 12 to 30 carbon atoms;
x is an integer from 0 to 3;
y is an integer from 1 to 4;
(The sum of x and y is equal to the valence of metal M)
The method in any one of said (1)-(5) represented by these.
(7) The method according to any one of (1) to (6), wherein the extracted metal carboxylate salt contains an aluminum carboxylate.
(8) Any of (1) to (7) above, wherein the metal carboxylate salt comprises aluminum stearate selected from the group consisting of aluminum monostearate, aluminum distearate, aluminum tristearate and combinations thereof The method of crab.
(9) The method further comprises the step of adding a continuous additive containing the extracted metal carboxylate salt to the reactor, and adding the continuous additive and the catalyst composition separately to the reactor. The method in any one of-(8).
(10) The method according to any one of (1) to (8), further comprising adding a catalyst compound to the reactor in combination with the continuous additive containing the extracted metal carboxylate salt.
(11) Any of the above (1) to (10), wherein the catalyst composition further comprises a carrier, the catalyst compound is a metallocene catalyst compound, and the metallocene catalyst compound and the carrier are combined together using initial wet impregnation. The method of crab.
(12) The catalyst composition further comprising a support and an activator, wherein the catalyst compound is a metallocene catalyst compound containing at least one atom selected from the group consisting of a titanium atom, a zirconium atom and a hafnium atom. The method according to any one of 1) to (10).
(13) The metallocene catalyst compound is (pentamethylcyclopentadienyl) (propylcyclopentadienyl) MX2, tetramethylcyclopentadienyl) (propylcyclopentadienyl) MX2, (tetramethylcyclopentadienyl) ( (Butylcyclopentadienyl) MX2, Me2Si (indenyl) 2MX2, Me2Si (tetrahydroindenyl) 2MX2, (n-propylcyclopentadienyl) 2MX2, (n-butylcyclopentadienyl) 2MX2, (1-methyl-3 -Butylcyclopentadienyl) 2MX2, HN (CH2CH2N (2,4,6-Me3phenyl)) 2MX2, HN (CH2CH2N (2,3,4,5,6-Me5phenyl)) 2MX2, (propylcyclopentadi) Enyl) (tetramethylcyclopentadienyl) MX2, (butylcyclopentadienyl) 2MX2, (propylcyclope) Tadienyl) 2MX2 and combinations thereof (wherein M is Zr or Hf and X is selected from the group consisting of F, Cl, Br, I, Me, Bnz, CH2SiMe3, C1-C5 alkyl and C1-C5 alkenyl) The method according to any one of (1) to (11) above, wherein the method is selected from the group consisting of:
(14) The catalyst composition includes a carrier and an activator, and the catalyst compound is (1-methyl-3-butylcyclopentadienyl) 2ZrX2 (where X is composed of F, Cl, Br, I and Me). The method according to any one of the above (1) to (10), which is a metallocene catalyst compound selected from the group consisting of:
(15) The catalyst composition includes a metallocene catalyst compound and at least one other catalyst compound selected from a Ziegler-Natta catalyst, a chromium-based catalyst, a metallocene catalyst, a Group 15 catalyst, and combinations thereof. The method according to any one of (1) to (10) above.
(16) The polymerization method according to any one of the above (1) to (15), which has increased catalyst productivity.
(17) A polymer product containing a polyolefin produced by the polymerization method according to any one of (1) to (16).
(18) The polymer according to (17), wherein the polymer has an increased resin bulk density compared to a polymer produced by the same method except that the metal carboxylate salt is not extracted. .
(19) A polymerization method for producing an ethylene / α-olefin copolymer comprising:
Ethylene and an α-olefin and a catalyst composition are contacted in a reactor under polymerization conditions to produce an ethylene / α-olefin copolymer, wherein the catalyst composition is extracted with the polymerization catalyst and a first extraction. The first extracted metal carboxylate salt comprising a metal carboxylate salt, obtained by extracting the metal carboxylate salt with an organic solvent having a dielectric constant at 25 ° C. of 3.0 or higher. Yes; and
A continuous additive comprising a second extracted metal carboxylate salt is added to the reactor, wherein the continuous additive and the catalyst composition are separately added to the reactor, and the second The extracted metal carboxylate salt is obtained by extracting the metal carboxylate salt with an organic solvent having a dielectric constant at 25 ° C. of 3.0 or higher:
The polymerization method.
(20) The method according to (19) above, wherein each of the first extracted metal carboxylate salt and the second extracted metal carboxylate salt contains essentially no free carboxylic acid.
(21) The metal carboxylate salt extracted to obtain the first extracted metal carboxylate salt and the second extracted metal carboxylate salt is aluminum monostearate, aluminum distearate, tristearic acid The method according to (19) or (20), which is independently selected from aluminum and combinations thereof.

Claims (18)

  1. A polymerization process comprising polymerizing an olefin in the presence of a catalyst composition and an extracted metal carboxylate salt in a reactor comprising:
    All SANYO obtained by extracting a metal carboxylate salt in an organic solvent in which the extracted metal carboxylates salts have a dielectric constant at 3.0 or greater 25 ° C.,
    The method, wherein the catalyst composition comprises a catalyst compound comprising a metallocene catalyst compound .
  2.   The method of claim 1, wherein the extracted metal carboxylate salt is essentially free of free carboxylic acid.
  3. Containing Yu Hanaresan of less than 1% by weight based on the total weight of said metal carboxylate salt extracted metal carboxylate salt is extracted, the method according to claim 1 or 2.
  4. The organic solvent is C 1 -C 10 alcohol, C 1 -C 10 ketones, C 1 -C 10 esters, C 1 -C 10 ethers, C 1 -C 10 alkyl halide, C 1 -C 10 alkyloxycarbonyl nitrile, C 1 -C 10 dialkyl sulfoxide and is selected from the group consisting of combinations thereof the method of claim 1 or 2.
  5. The metal carboxylate salt has the formula:
    MQ x (OOCR) y
    (Where M is a Group 13 metal from the Periodic Table of Elements;
    Q is a halogen, hydroxy, alkyl, alkoxy, aryloxy, siloxy, silane or sulfonate group;
    R is a hydrocarbyl group having 12 to 30 carbon atoms;
    x is an integer from 0 to 3;
    y is an integer from 0 to 3 ; and the sum of x and y is equal to the valence of the metal M)
    The method of Claim 1 or 2 represented by these.
  6.   The method of claim 1 or 2, wherein the extracted metal carboxylate salt comprises an aluminum carboxylate.
  7. Adding a continuous additive comprising the extracted metal carboxylate salt to the reactor, and adding the continuous additive and the catalyst composition separately to the reactor ;
    The continuous additive comprises at least one of a fatty acid amine, an amide-hydrocarbon or ethoxylated amide compound, a carboxylate compound, a fatty acid-metal complex; an alcohol, an ether, a sulfate compound, and a metal oxide. Or the method of 2.
  8.   3. The method of claim 1 or 2, further comprising adding a catalyst compound to the reactor in combination with a continuous additive comprising the extracted metal carboxylate salt.
  9. Wherein wherein the catalyst composition further carriers, the bringing together the metallocene catalyst compound and a carrier with a first onset wet impregnation, said initial wet impregnation, where dissolving the catalyst composition in the organic solvent The method according to claim 1 or 2, comprising:
  10.   The catalyst composition further comprises a support and an activator, and the catalyst compound is a metallocene catalyst compound containing at least one atom selected from the group consisting of a titanium atom, a zirconium atom and a hafnium atom. The method described in 1.
  11. The catalyst compound is a metallocene compound, and the metallocene compound is (pentamethylcyclopentadienyl) (propylcyclopentadienyl) MX 2 , tetramethylcyclopentadienyl) (propylcyclopentadienyl) MX 2 , (tetra Methylcyclopentadienyl) (butylcyclopentadienyl) MX 2 , Me 2 Si (indenyl) 2 MX 2 , Me 2 Si (tetrahydroindenyl) 2 MX 2 , (n-propylcyclopentadienyl) 2 MX 2 (N-butylcyclopentadienyl) 2 MX 2 , (1-methyl-3-butylcyclopentadienyl) 2 MX 2 , ( propylcyclopentadienyl) (tetramethylcyclopentadienyl) MX 2 , ( Butylcyclopentadienyl) 2 MX 2 , (propylcyclopentadienyl) 2 MX 2 and combinations thereof (where M is Zr or A hf, X is F, Cl, Br, I, Me, Bnz, is selected from CH 2 SiMe 3, C1-C5 alkyl and C1-C5 group consisting selected from the group consisting of alkenyl), claim The method according to 1 or 2.
  12. The catalyst compound is HN (CH 2 CH 2 N (2,4,6-Me3 phenyl)) 2 MX 2 Or HN (CH 2 CH 2 N (2,3,4,5,6-Me Five Phenyl)) 2 MX 2 The method according to claim 1, comprising:
  13. The catalyst composition includes a support and an activator, and the catalyst compound is (1-methyl-3-butylcyclopentadienyl) 2 ZrX 2 (where X is a group consisting of F, Cl, Br, I and Me). The method according to claim 1 or 2, wherein the compound is a metallocene catalyst compound selected from.
  14. 3. The catalyst composition of claim 1 or 2, wherein the catalyst composition comprises a metallocene catalyst compound and at least one other catalyst compound selected from a Ziegler-Natta catalyst, a chromium-based catalyst , a Group 15 catalyst, and combinations thereof. The method described.
  15.   3. A process according to claim 1 or 2 having an enhanced catalyst productivity compared to the same process except that the metal carboxylate salt is not extracted.
  16. A polymerization process for producing an ethylene / α-olefin copolymer comprising:
    Ethylene and an α-olefin and a catalyst composition are contacted in a reactor under polymerization conditions to produce an ethylene / α-olefin copolymer, wherein the catalyst composition is extracted with the polymerization catalyst and a first extraction. The first extracted metal carboxylate salt comprising a metal carboxylate salt, obtained by extracting the metal carboxylate salt with an organic solvent having a dielectric constant at 25 ° C. of 3.0 or higher. And; adding to the reactor a continuous additive comprising a second extracted metal carboxylate salt, wherein the continuous additive and the catalyst composition are separately added to the reactor, The second extracted metal carboxylate salt is extracted with an organic solvent having a dielectric constant at 25 ° C. of 3.0 or higher. It is obtained by:
    Look at including it,
    The catalyst composition comprises a metallocene catalyst compound;
    The continuity additive, fatty acid amines, amides - hydrocarbon or ethoxylated amide compounds, carboxylate compounds, fatty acid - metal complex, at least 1 Tsuo含 free of alcohols, ethers, sulfate compounds, and metal oxides, wherein the polymer Method.
  17. 17. The method of claim 16 , wherein the first extracted metal carboxylate salt and the second extracted metal carboxylate salt are each essentially free of free carboxylic acid.
  18. The metal carboxylate salts extracted to obtain the first extracted metal carboxylate salt and the second extracted metal carboxylate salt are aluminum monostearate, aluminum distearate, aluminum tristearate and the like The method according to claim 16 or 17 , wherein the method is independently selected from a combination of:
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